Germicidal detergent



Patented-Nov. 29, 1938 Halvor 0. Halvorson, and

John L. Wilson, St.

Paul, and Erling J. Ordal, Minneapolis, Minn.

ore to Economics Laboratory 811 Paul, Minn Inc., St:

a corporation of Delaware No Drawing. Application May 8, 1935,

Serial No. 20,508

4 Claims.

This invention relates to new germicidal detergent compositions.

Thenew compositions contain alkalies or butter salts, soaps, and azochloramid, in such propor- 5 tions that when, for example, a solution is made of the composition, containing from to 3% of the composition, the solution will be an effective germicidal detergent, and the soap and the azochloramid will each form only a small frac- 0 tion of 1% of the solution.

Azochloramid is an abbreviated name for the compound N N dichloro-azodicarbonamidine, NH2.(NC1) :C.l l:N.C:(NC1).NI -Iz is known to have germicidal properties, but when used together with soap in solutions which are alkaline with suitable alkalies or buffer salts, the azochloramid and the soap appear to have a mutual activating action upon each other, or the azochloramid, which by itself is an excellent germicidal agent, is activated to a very considerable extent by the soap in such an alkaline solution.

It has been found that the compositions may contain alkalies which give a high alkalinity or pH value, and that the azochloramid is not rendered inactive by such high alkalinities, so that compositions can readily be made of high alkalinity, which is important from a detergent standpoint as well as from a bacteriological standpoint. The compositions are moreover effective as germicidal detergents at relatively low pH values. The range of pH values of the solutions of the new compositions may thus include low pH values of around 7 to 10 or 11, as well as higher pH values materially in' excess thereof.

The buffer salts which are used in the new compositionare alkaline salts or alkalies, such as carbonates, phosphates -or silicates, etc., used in such amounts and proportions final solution the desired pH value. Among such bufier salts may be mentioned sodium carbonate and bicarbonate, mono-sodiumand iii-sodium phosphate, sodium silicates, etc.

In using these bufier salts, in making the new composition, the proper pH is obtained by a se-' lection of the bufier 'salts employed which may, in some cases, be a single salt or salts of the same acid, such as sodium carbonate and bicarbonate, or salts of different acids, etc. For example, the proper pH may be obtained by the use of a mix- )0 ture of various phosphates and carbonates, or

various phosphates and silicates, or carbonates and silicates, or by mixtures of phosphates, carbonates and silicates, as well as by mixtures of various phosphates alone, or carbonates alone, or i5 silicates alone. Similarly, other salts besides as will give to the phosphates, carbonates and silicates may be used Different soaps can be used in the composition of the present invention, including ordi within the range of from ed for obdefined by e resulting solution rather than by 5 particular salts or combinations of salts emparticular salt or mixtures of to give the nary soaps such as tallow soap, or resin soaps such as sodium resinate.

In general, the amount of soap employed, in

proportion to the amount of bufier salts, will be such that the soap, will be present to of only a small solution, and the amount of azochlo also be only a small traction of 1% solution.

Solutions made from the proportions and amounts such the extent percentage of. 1% in the final ramid. will of such a new composition, in as those above.

mentioned, are excellent detergents and exhibit sufiicient germicidal properties so tha be used as germicides.

t they can In general, the solutions made with the new composition will contain from around to 3% of the composition.

The new composition pounded and marketed in the form powder, containing the various ingredi iorm or an intimate and is advantageously com- 01 a dry ents in the homogenous admixture,

such that a definite weight of the powder can be used to give a solution of definite strength or proportions of the diilerent ingredients. Such a dry mixture of the ingredients can be readilyproduced, handled, shipped and stored, and a deflnite amount measured out for use in germicidal detergent solutions.

In testing the solutions'or the new composition,

producing we have used the following test: The dry mixture, containing the ingredients of the composition, is made into a solution 01' from strength. To 5 cc. of this solution is of a 24 hour culture 01' the standard /z% to 1% added cc. test organism. Staphylococcus aureus (Insecticide Board strain). Before the culture is added to the test solution, itis brought to the requiredv temperature; the temperature we havecused the culture has been in the test soluti has been 37 C. or such other temperature as indicated. After on for five minutes, a 4 mm. loopiul is removed and added to a tube of molten agar at a temperature of 45 C.

and the mixture is poured into a The plates are incubated for 48 hours,

Petri plate.

at the end of which time a count is made of the colonies appearing on the plate. The number of organisms originally added to the test solution is in the neighborhood of five hundred millions (500,- 000,000). If no organisms are killed, the loopful removed will contain an excess of 10,000 organisms, and therefore the number of colonies appearing on the plates will be in excess of 10,000. If some of the organisms are killed, the number of colonies appearing on the plates will be less than 10,000. In the data reported in the following examples the numbers indicate the colonies appearing on the test plate after 48 hours of incubation. Similar tests were made using Ebe thella typhi (Hopkins strain.)

The invention will be illustrated by the following examples.

The composition was made of sodium resinate soap, azochloramid, and buffer salts, using equal azochloramid and buifer salts showed a germicidal activity, this was markedly increased when sodium resinate was also present, and effective antiseptic or germicidal solutions were obtained with a strength of azochloramid which was ineffective in the absence of the sodium resinate, thus showing the activating action of the sodium resinate upon the azochloramid, or the mutual activation of these substances by each other.

As further illustrating the invention, tests were made with tallow soap, as the soap constituent of the composition, in comparison with solutions free from azochloramid,and solutions containing a-zochloramid but free from tallow soap. The tests were carried out at a temperature of 37 C. with the same organism above referred to and with the use of a 1% solution of sodium silicate (NazSiO3.5H20) giving a pH of about 12.3. The solutions tested and the results obtained are inparts of sodium carbonate and sodium bicarbonate dicated by the following table: as the buffer salts to give a pH of 9.7 in a 1% solution of the composition, and using amounts of Plate counts sodium resinate and of azochloramid indicated solution test-ed in the following table, which gives the results of 5min 10min tests carried out at a temperature 37 C. with Staphylococcus aureus (24 hour culture) 1% bufier 7,000 1, 500 1% bufler+0.0l% tallow soap 2, 000 300 1% bufler+0.003% azochlorami 200 20 Flam counts 1%h1bufierg0.01% tallow soap+0.003% azoloo 0 C ram! tested 1 ghenol (as control) 1 o 5 min. 10 min. l/ phenol (as control) 10 2 1% buffer-+01% sodium resinate 5,000 a, 000 From the foregoing examples it will be seen that ii?? gf gigg fi a ggg ggfig 59 .the azochloramid is used in only small fractions llgilolrlamiili n 5 1 of 1% of the final solution and that the soap 1s 11 8S 00!! 10 g g g (as control) 100 8 also used in small fractions of 1% of the final solution, although in amounts considerably larger From this table it will be noted that the buffer salt and sodium resinate alone were not effective, while the effectiveness of the azochloramid was markedly increased by the presence of the sodium resinate in the alkaline solution. The two phenol solutions included in the above table are given for purposes of comparison, as the control.

As further illustrative of the invention, tests were made in which azochloramid was used in different proportions with a bufier solution, and without sodium resinate, and in which sodium resinate was used with the buffersolution, without the azochloramid, as well as tests in which both sodium resinate and azochloramid were used with the buffer salts. These tests were carried out at a temperature of 45 C. with a Staphylococcus aureus organism (24 hour culture), using a buffer solution made up of equal parts of sodium carbonate and sodium bicarbonate which would give a pH of 9.7 in 1% solution. The following results were obtained:

Plate counts Solution tested 5min.

9'1" e s o O a From this table it will be a... that, while the 10 min.

In preparing the new composition for the mar- I ket, it is advantageously prepared in the form of a dry powder or mixture containing the diiferent ingredients in the proper porportions. Such a dry powder or mixture can be readily manufactured, stored and shipped, and can be readily used for detergent purposes, where a detergent germicide is desired, merely by adding the composition to water in the proper proportions and using the resulting solution as a germicidal detergent.

While, in the above examples, only two specific soaps are mentioned, it will be understood that other soaps can be used. The nature and amount of the buffer salt, or of the different buffer salts, used, can be varied, and the detergent action of the solution somewhat controlled thereby, as well as by the nature and amount of the soap used. It is one advantage of the present invention, as above mentioned, that a wide pH range can be used without interfering with the efiectiveness of the germicidal properties of the solution, so that high pH solutions can be produced and used.

The new compositions are useful for many as in hotels and restaurants for dish-washing and other purposes, and in various industries such as the beverage and dairy industries where, for example, the washing and sterilizing of bottles and containers is important. I

We claim:

1. A germicidal detergent composition comprispurposes, as in hospitals or institutions, as well 4 the azochloramid being present in amounts in-- ing bufler salts, soap, and azochloramid, said composition being soluble in water, and a solution made therefrom, and containing from to 3% of the composition, containing only a small fraction of 1% of the soap and azochlcramid,

suflicient to rendersuch solution germicidal in the absence of the soap.

2. A germicidal detergent composition in the form ofsa dry mixture of bufier salts, soap and azochloramid, the composition being made up for the most part of buffer salts, and containing a relatively smaller amount of the azochloramid and of the soap, and the composition being adapted, when dissolved in water to i'orm a solution containing from around to 3% of the composition, to give an active germicidal detergent composition, the azochloramid being present in amounts insuflicient to render such solution germicidal in the absence of the soap.

3. A germicidal detergent composition in the form of a dry mixture of buffer salts, soap and azochloramid, the composition being made up for the most part of bufier salts, and containing a relatively smaller amount of the soap, and a small amount ofthe azochloramid, such that when the composition is dissolved in water to form a solution containing sufflcient of the composition to give an eifective detergent solution, the solution will be actively germicidal. andthe azochloramid will be present in an amount less than that required for the solution to be germicidal in the absence of the soap.

4. A germicidal detergent solution containing less than 3% of buffer salts, a fraction of 1% of a soap, and a small amount of azochloramid less than the amount normally soluble in distilled water at the temperature of the solution, and less than that required to make the solution germicidal in the absence of the soap.

JOHN -L. WILSON. ERLING J. ORDAL. 

